Morpholine derivatives in viscose spinning



Patented Jan. 31, 1950 MORPHOLINE DERIVATIVES IN VISCOSE SPINNING Kenneth R. Brown, West Chester, Pa., assignor to Atlas Powder Company, Wilmington, Del., a

corporation of Delaware No Drawing. Application October 26, 1948, Serial No. 56,668

8 Claims.

The present invention relates to improvements in the manufacture of regenerated cellulose.

The invention finds particular application in the viscose process for manufacturing filaments, films and other shapes of regenerated cellulose. In this process a cellulose xanthate solution is extruded through an orifice in a suitable jet or spinner into a coagulating and regenerating bath which conventionally contains sulfuric acid and salts such as zinc sulfate in aqueous solution. In the course of operation, the jets or spinners tend to become obstructed and encrusted with solid materials which change the shape and size of the discharge openings thereby deforming or interrupting the extruded stream and causing irregularities or breaks in the regenerated product. When this condition of fouling of the jets or spinners occurs, it is necessary to stop the machine and dismantle and clean the jets or spinners. It is not only costly to interrupt production in this manner, but the quality of a large quantity of the ,product may be seriously impaired before the condition becomes sufficiently apparent for the operator to stop the machine. The most successful attack on this fouling problem has consisted in employing specific, empirically selected anti-fouling agents in the spin bath, the viscose solution or both. The agents, which may be of various chemical types, are selected because of their proven ability to inhibit the obstruction or encrustation of the jets or spinners.

An object of the present invention is to provide an improved cellulose regenerating process employing a novel anti-fouling agent.

A particular object is to provide an improvement in the viscose process wherein certain soluble and stable morpholine or thiomorpholine derivatives are employed as anti-fouling agents.

In accordance with the present invention the viscose (cellulose Xanthate) solution or the spin bath or both have included therein a small proportion of a compound, or mixture of compounds,

of the type C2H4 X\ 2 OSOQOR wherein,

ber of carbon atoms in the three Rs being from 8 to 2'0.

Compounds of this type can be prepared by the methods of Niederl and his associates as described, for example, in J, A Q. S, 63, 1476; 66,

840; 66, 1610; 67, 1227; 68, 714; 70, 618. The morpholine derivatives are preferably made from dichlorodiethyl ether, a primary aliphatic amine containing a 6 to 24 carbon atom chain, and a dialkyl sulfate. The thiomorpholine (also called thiamorpholine) derivatives are preferably made by substituting dichloro-diethyl sulfide (mustard gas) for the ether in the morpholine reaction, while the sulfoxides and sulfones can be obtained by first oxidizing the mustard gas to the desired state.

Examples of compounds of this group are hexyl-methyl morpholinium methosulfate; octyl-ethyl-morpholinium methosulfate; laurylmethyl-morpholinium methosulfate; cetyl-methyl-morpholinium methosulfate; lauryl-methylmorpholinium ethosul'fate; lauryl-ethyl-morpholinium ethosulfate; hexyl-methyl-thiomorpholinium methosulfate; lauryl-methyl-thiomorpholinium methosulfate; cetyl-ethyl-thiomorpholinium ethosulfate; lauryl-methyl-loxythiomorpholinium methosulfate; and lauryl-methyll-dioxythiomorpholinium methosulfate.

Of this class of anti-fouling compounds, those with a total of 16 carbon atoms in the three alkyl groups are preferred because of greater solubility in the spinning media. All of the compounds exhibit stability in both alkalinge media such as the viscose solution and in acid media such as the regenerating solution in the spin bath. These compounds will inhibit to a valuable extent the fouling of the jets or spinners in a viscose process.

In practicing the invention, a small proportion, suitably from 0.001 to 0.1%, of the antifouling compound or a mixture of two or more such compounds is dissolved either in the viscose solution or in the regenerating bath and the process performed in the well-known manner in other respects.

Example 1 Extrude an ordinary viscose solution through a spinneret in the conventional manner into a conventional spin bath containing an aqueous solution of sulfuric acid and zinc sulphate and an addition of 0.01% by weight of N-lauryl-N- methyl-morpholinium methosulfate. If desired, the spin bath can contain glucose, other salts such as ammonium and sodium sulfates, and various other ingredients in accordance with usual practice.

Example 2 Make up an ordinary viscose solution and dissolve therein 0.002% by weight of N-lauryl-N- methyl-morpholinium methosulfate. Extrude this solution through a spinneret in the conventional manner into a conventional spin bath containing sulfuric acid and zinc sulfate. Additional ingredients can be included in the spin bath in accordance with usual practice.

When operating in accordance with the present invention, the number of interruptions to production, due to fouling of the spinners or jets, is very materially reduced and the regenerated cellulose products are more uniform and of higher quality by comparison with the results obtained in an otherwise identical operation, but omitting the anti-fouling agent of this inven tion.

The invention is not to be taken as limited to the details of the specific illustrations given, but is of more general application as will be apparent to those skilled in the art. It should be noted that it is not essential to employ pure chemical individuals as the anti-fouling agents, since valuable results are obtained using mixtures prepared by adding together difierent pure compounds of the class contemplated, or mixtures ooourring as the result of using mixed reactants (such as commercial grades of the aliphatic amines) in the manufacture of the anti-fouling agent.

What is claimed is:

1. The process for manufacturing regenerated cellulose articles which comprises extruding a viscose solution through an orifice into a regenerating bath in the presence of a small proportion of at least one compound of the type C2114 X\ IRQ' OSOzOR emf wherein,

Bil

X=a radical selected from the group consisting of oxygen, sulfur, sulfoxide, and sulfone. R=an alkyl group containing from 1 to 24 carbon atoms, the three Rs may be different alkyl groups Within said limit, and the total number of carbon atoms in the three Rs being from 8 to 26.

2. The process of claim 1 wherein the said compound is incorporated originally in the viscose solution.

3. The process of claim 2 wherein the proportion of said compound in the viscose solution is from 0.001% to 0.1% by weight.

4. The process of claim 1 wherein the said compound is incorporated originally in the regenerating bath.

5. The process of claim 4 wherein the proportion of said compound in the regenerating bath is from 0.001% to 0.1% by weight.

6. The process for manufacturing regenerated cellulose articles which comprises extruding a viscose solution through an orifice into a regenerating bath in the presence of a small proportion of N-lauryl-N-methyl-morpholinium methosulfate.

7. The process of claim 6 wherein the N- lauryl-N-methyl-morpholinium methosulfatc is incorporated originally in the viscose solution in the proportion of from 0.001% to 0.1% by weight.

8. The process of claim 6 wherein the N- 1auryl-N-rnethyl-morpholinium methosulfate is incorporated originally in the regenerating bath in the proportion of from 0.001% to 0.1% by weight.

KENNETH R. BROWN.

No references cited. 

1. THE PROCESS FOR MANUFACTURING REGENERATED CELLULOSE ARTICLES WHICH COMPRISES EXTRUDING A VISCOSE SOLUTION THROUGH AN ORIFICE INTO A REGENERATING BATH IN THE PRESENCE OF A SMALL PROPORTION OF AT LEAST ONE COMPOUND OF THE TYPE 